Influence of electrolyte cations on electron transport and electron transfer in dye-sensitized solar cells

The influence of different electrolyte cations ((Li+, Na+, Mg2+, tetrabutyl ammonium (TBA+)) on the TiO2 conduction band energy (Ec) the effective electron lifetime (τn), and the effective electron diffusion coefficient (Dn) in dye-sensitized solar cells (DSCs) was studied quantitatively. The separation between Ec and the redox Fermi level, EF,redox, was found to decrease as the charge/radius ratio of the cations increased. Ec in the Mg2+ electrolyte was found to be 170 meV lower than that in the Na+ electrolyte and 400 meV lower than that in the TBA+ electrolyte. Comparison of Dn and τn in the different electrolytes was carried out by using the trapped electron concentration as a measure of the energy difference between Ec and the quasi-Fermi level, nEF, under different illumination levels. Plots of Dn as a function of the trapped electron density, nt, were found to be relatively insensitive to the electrolyte cation, indicating that the density and energetic distribution of electron traps in TiO2 are similar in all of the electrolytes studied. By contrast, plots of τn versus nt for the different cations showed that the rate of electron back reaction is more than an order of magnitude faster in the TBA+ electrolyte compared with the Na+ and Li+ electrolytes. The electron diffusion lengths in the different electrolytes followed the sequence of Na+ > Li+ > Mg2+ > TBA+. The trends observed in the AM 1.5 current–voltage characteristics of the DSCs are rationalized on the basis of the conduction band shifts and changes in electron lifetime.

Multi-level knowledge transfer in software development outsourcing projects : the agency theory view

In recent years, software development outsourcing has become even more complex. Outsourcing partner have begun‘re- outsourcing’ components of their projects to other outsourcing companies to minimize cost and gain efficiencies, creating a multi-level hierarchy of outsourcing. This research in progress paper presents preliminary findings of a study designed to understand knowledge transfer effectiveness of multi-level software development outsourcing projects. We conceptualize the SD-outsourcing entities using the Agency Theory. This study conceptualizes, operationalises and validates the concept of Knowledge Transfer as a three-phase multidimensional formative index of 1) Domain knowledge, 2) Communication behaviors, and 3) Clarity of requirements. Data analysis identified substantial, significant differences between the Principal and the Agent on two of the three constructs. Using Agency Theory, supported by preliminary findings, the paper also provides prescriptive guidelines of reducing the friction between the Principal and the Agent in multi-level software outsourcing.

Disclosure obligations on ex parte application for freezing order - duty of practitioners to the court - failure to comply with duty - serious dereliction of duty to court - supplemental order for costs against solicitors personally

The decision of Applegarth J in Heartwood Architectural & Joinery Pty Ltd v Redchip Lawyers [2009] QSC 195 (27 July 2009) involved a costs order against solicitors personally. This decision is but one of several recent decisions in which the court has been persuaded that the circumstances justified costs orders against legal practitioners on the indemnity basis. These decisions serve as a reminder to practitioners of their disclosure obligations when seeking any interlocutory relief in an ex parte application. These obligations are now clearly set out in r 14.4 of the Legal Profession (Solicitors) Rule 2007 and r 25 of 2007 Barristers Rule. Inexperience or ignorance will not excuse breaches of the duties owed to the court.

Hybrid graphene and graphitic carbon nitride nanocomposite : gap opening, electron–hole puddle, interfacial charge transfer, and enhanced visible light response

Opening up a band gap and finding a suitable substrate material are two big challenges for building graphene-based nanodevices. Using state-of-the-art hybrid density functional theory incorporating long range dispersion corrections, we investigate the interface between optically active graphitic carbon nitride (g-C3N4) and electronically active graphene. We find an inhomogeneous planar substrate (g-C3N4) promotes electronrich and hole-rich regions, i.e., forming a well-defined electron−hole puddle, on the supported graphene layer. The composite displays significant charge transfer from graphene to the g-C3N4 substrate, which alters the electronic properties of both components. In particular, the strong electronic coupling at the graphene/g-C3N4 interface opens a 70 meV gap in g-C3N4-supported graphene, a feature that can potentially allow overcoming the graphene’s band gap hurdle in constructing field effect transistors. Additionally, the 2-D planar structure of g-C3N4 is free of dangling bonds, providing an ideal substrate for graphene to sit on. Furthermore, when compared to a pure g-C3N4 monolayer, the hybrid graphene/g-C3N4 complex displays an enhanced optical absorption in the visible region, a promising feature for novel photovoltaic and photocatalytic applications.

Hybrid graphene/titania nanocomposite : interface charge transfer, hole doping, and sensitization for visible light response

We demonstrated for the first time by large-scale ab initio calculations that a graphene/titania interface in the ground electronic state forms a charge-transfer complex due to the large difference of work functions between graphene and titania, leading to substantial hole doping in graphene. Interestingly, electrons in the upper valence band can be directly excited from graphene to the conduction band, that is, the 3d orbitals of titania, under visible light irradiation. This should yield well-separated electron−hole pairs, with potentially high photocatalytic or photovoltaic performance in hybrid graphene and titania nanocomposites. Experimental wavelength-dependent photocurrent generation of the graphene/titania photoanode demonstrated noticeable visible light response and evidently verified our ab initio prediction.

Protection of structural systems and mechanisms from catastrophic and life-threatening failure caused by unforeseeable events

Structural framing systems and mechanisms designed for normal use rarely possess adequate robustness to withstand the effects of large impacts, blasts and extreme earthquakes that have been experienced in recent times. Robustness is the property of systems that enables them to survive unforeseen or unusual circumstances (Knoll & Vogel, 2009). Queensland University of Technology with industry collaboration is engaged in a program of research that commenced 15 years ago to study the impact of such unforeseeable phenomena and investigate methods of improving robustness and safety with protective mechanisms embedded or designed in structural systems. This paper highlights some of the research pertaining to seismic protection of building structures, rollover protective structures and effects of vehicular impact and blast on key elements in structures that could propagate catastrophic and disproportionate collapse.

Rebuilding housing after a disaster : factors for failure

Unlike most normal construction projects, post-disaster housing projects are diverse in nature, have unique socio-cultural and economical requirements, and are extremely dynamic and thus necessitate a meaningful and dynamic response. Post-disaster reconstruction practices that lack a strategy compatible with the severity of disaster, community culture, socio-economic requirements, environmental condition, government legislations, and technical and technological situations, often fail to operate and respond effectively to the needs of the wider affected population. Factors that frequently pose real threats to the eventual success of reconstruction projects are rarely given appropriate consideration when designing such projects. Research into past reconstruction practices has shown that ignoring these factors altogether or failing to give them meaningful consideration can affect housing reconstruction projects. In other words, they either miss their targets altogether or undergo serious modifications after their occupancy, subsequently resulting in an overall loss of project resources. This article touches upon the common factors that negatively impact the outcome of such projects.

Risk modelling in quality clinical registries : Monitoring lesion treatment failure rate in percutaneous coronary interventions

Aims: This paper describes the development of a risk adjustment (RA) model predictive of individual lesion treatment failure in percutaneous coronary interventions (PCI) for use in a quality monitoring and improvement program. Methods and results: Prospectively collected data for 3972 consecutive revascularisation procedures (5601 lesions) performed between January 2003 and September 2011 were studied. Data on procedures to September 2009 (n = 3100) were used to identify factors predictive of lesion treatment failure. Factors identified included lesion risk class (p < 0.001), occlusion type (p < 0.001), patient age (p = 0.001), vessel system (p < 0.04), vessel diameter (p < 0.001), unstable angina (p = 0.003) and presence of major cardiac risk factors (p = 0.01). A Bayesian RA model was built using these factors with predictive performance of the model tested on the remaining procedures (area under the receiver operating curve: 0.765, Hosmer–Lemeshow p value: 0.11). Cumulative sum, exponentially weighted moving average and funnel plots were constructed using the RA model and subjectively evaluated. Conclusion: A RA model was developed and applied to SPC monitoring for lesion failure in a PCI database. If linked to appropriate quality improvement governance response protocols, SPC using this RA tool might improve quality control and risk management by identifying variation in performance based on a comparison of observed and expected outcomes.

Anisotropic damage mechanics as a novel approach to improve pre-and post-failure borehole stability analysis

Anisotropic damage distribution and evolution have a profound effect on borehole stress concentrations. Damage evolution is an irreversible process that is not adequately described within classical equilibrium thermodynamics. Therefore, we propose a constitutive model, based on non-equilibrium thermodynamics, that accounts for anisotropic damage distribution, anisotropic damage threshold and anisotropic damage evolution. We implemented this constitutive model numerically, using the finite element method, to calculate stress–strain curves and borehole stresses. The resulting stress–strain curves are distinctively different from linear elastic-brittle and linear elastic-ideal plastic constitutive models and realistically model experimental responses of brittle rocks. We show that the onset of damage evolution leads to an inhomogeneous redistribution of material properties and stresses along the borehole wall. The classical linear elastic-brittle approach to borehole stability analysis systematically overestimates the stress concentrations on the borehole wall, because dissipative strain-softening is underestimated. The proposed damage mechanics approach explicitly models dissipative behaviour and leads to non-conservative mud window estimations. Furthermore, anisotropic rocks with preferential planes of failure, like shales, can be addressed with our model.

Proton-transfer compounds with 4-amino-N-(4,6-dimethylpyrimidin-2-yl)benzenesulfonamide (sulfamethazine): the structures and hydrogen-bonding in the salts with 5-nitrosalicylic acid and picric acid

The structures of the anhydrous proton-transfer compounds of the sulfa drug sulfamethazine with 5-nitrosalicylic acid and picric acid, namely 2-(4-aminobenzenesulfonamido)-4,6-dimethylpyrimidinium 2-hydroxy-5-nitrobenzoate, C12H15N4O2S(+)·C7H4NO4(-), (I), and 2-(4-aminobenzenesulfonamido)-4,6-dimethylpyrimidinium 2,4,6-trinitrophenolate, C12H15N4O2S(+)·C6H2N3O7(-), (II), respectively, have been determined. In the asymmetric unit of (I), there are two independent but conformationally similar cation-anion heterodimer pairs which are formed through duplex intermolecular N(+)-H...Ocarboxylate and N-H...Ocarboxylate hydrogen-bond pairs, giving a cyclic motif [graph set R2(2)(8)]. These heterodimers form separate and different non-associated substructures through aniline N-H...O hydrogen bonds, one one-dimensional, involving carboxylate O-atom acceptors, the other two-dimensional, involving both carboxylate and hydroxy O-atom acceptors. The overall two-dimensional structure is stabilized by π-π interactions between the pyrimidinium ring and the 5-nitrosalicylate ring in both heterodimers [minimum ring-centroid separation = 3.4580 (8) Å]. For picrate (II), the cation-anion interaction involves a slightly asymmetric chelating N-H...O R2(1)(6) hydrogen-bonding association with the phenolate O atom, together with peripheral conjoint R1(2)(6) interactions between the same N-H groups and O atoms of the ortho-related nitro groups. An inter-unit amine N-H...Osulfone hydrogen bond gives one-dimensional chains which extend along a and inter-associate through π-π interactions between the pyrimidinium rings [centroid-centroid separation = 3.4752 (9) Å]. The two structures reported here now bring to a total of four the crystallographically characterized examples of proton-transfer salts of sulfamethazine with strong organic acids.

Fixed failure rate ambiguity validation methods for GPS and compass

Ambiguity resolution plays a crucial role in real time kinematic GNSS positioning which gives centimetre precision positioning results if all the ambiguities in each epoch are correctly fixed to integers. However, the incorrectly fixed ambiguities can result in large positioning offset up to several meters without notice. Hence, ambiguity validation is essential to control the ambiguity resolution quality. Currently, the most popular ambiguity validation is ratio test. The criterion of ratio test is often empirically determined. Empirically determined criterion can be dangerous, because a fixed criterion cannot fit all scenarios and does not directly control the ambiguity resolution risk. In practice, depending on the underlying model strength, the ratio test criterion can be too conservative for some model and becomes too risky for others. A more rational test method is to determine the criterion according to the underlying model and user requirement. Miss-detected incorrect integers will lead to a hazardous result, which should be strictly controlled. In ambiguity resolution miss-detected rate is often known as failure rate. In this paper, a fixed failure rate ratio test method is presented and applied in analysis of GPS and Compass positioning scenarios. A fixed failure rate approach is derived from the integer aperture estimation theory, which is theoretically rigorous. The criteria table for ratio test is computed based on extensive data simulations in the approach. The real-time users can determine the ratio test criterion by looking up the criteria table. This method has been applied in medium distance GPS ambiguity resolution but multi-constellation and high dimensional scenarios haven't been discussed so far. In this paper, a general ambiguity validation model is derived based on hypothesis test theory, and fixed failure rate approach is introduced, especially the relationship between ratio test threshold and failure rate is examined. In the last, Factors that influence fixed failure rate approach ratio test threshold is discussed according to extensive data simulation. The result shows that fixed failure rate approach is a more reasonable ambiguity validation method with proper stochastic model.

Design of an experimental apparatus to analyse bagasse behaviour in a chute

Pressure feeder chutes are pieces of equipment used in sugar cane crushing to increase the amount of cane that can be put through a mill. The continuous pressure feeder was developed with the objective to provide a constant feed of bagasse under pressure to the mouth of the crushing mills. The pressure feeder chute is used in a sugarcane milling unit to transfer bagasse from one set of crushing rolls to a second set of crushing rolls. There have been many pressure feeder chute failures in the past. The pressure feeder chute is quite vulnerable and if the bagasse throughput is blocked at the mill rollers, the pressure build-up in the chute can be enormous, which can ultimately result in failure. The result is substantial damage to the rollers, mill and chute construction, and downtimes of up to 48 hours can be experienced. Part of the problem is that the bagasse behaviour in the pressure feeder chute is not understood well. If the pressure feeder chute behaviour was understood, then the chute geometry design could be modified in order to minimise risk of failure. There are possible avenues for changing pressure feeder chute design and operations with a view to producing more reliable pressure feeder chutes in the future. There have been previous attempts to conduct experimental work to determine the causes of pressure feeder chute failures. There are certain guidelines available, however pressure feeder chute failures continue. Pressure feeder chute behaviour still remains poorly understood. This thesis contains the work carried out between April 14th 2009 and October 10th 2012 that focuses on the design of an experimental apparatus to measure forces and visually observe bagasse behaviour in an attempt to understand bagasse behaviour in pressure feeder chutes and minimise the risk of failure.

The effect of exercise training on sleep quality in heart failure

Background: Heart failure is a serious condition estimated to affect 1.5-2.0% of the Australian population with a point prevalence of approximately 1% in people aged 50-59 years, 10% in people aged 65 years or more and over 50% in people aged 85 years or over (National Heart Foundation of Australian and the Cardiac Society of Australia and New Zealand, 2006). Sleep disturbances are a common complaint of persons with heart failure. Disturbances of sleep can worsen heart failure symptoms, impair independence, reduce quality of life and lead to increased health care utilisation in patients with heart failure. Previous studies have identified exercise as a possible treatment for poor sleep in patients without cardiac disease however there is limited evidence of the effect of this form of treatment in heart failure. Aim: The primary objective of this study was to examine the effect of a supervised, hospital-based exercise training programme on subjective sleep quality in heart failure patients. Secondary objectives were to examine the association between changes in sleep quality and changes in depression, exercise performance and body mass index. Methods: The sample for the study was recruited from metropolitan and regional heart failure services across Brisbane, Queensland. Patients with a recent heart failure related hospital admission who met study inclusion criteria were recruited. Participants were screened by specialist heart failure exercise staff at each site to ensure exercise safety prior to study enrolment. Demographic data, medical history, medications, Pittsburgh Sleep Quality Index score, Geriatric Depression Score, exercise performance (six minute walk test), weight and height were collected at Baseline. Pittsburgh Sleep Quality Index score, Geriatric Depression Score, exercise performance and weight were repeated at 3 months. One hundred and six patients admitted to hospital with heart failure were randomly allocated to a 3-month disease-based management programme of education and self-management support including standard exercise advice (Control) or to the same disease management programme as the Control group with the addition of a tailored physical activity program (Intervention). The intervention consisted of 1 hour of aerobic and resistance exercise twice a week. Programs were designed and supervised by an exercise specialist. The main outcome measure was achievement of a clinically significant change (.3 points) in global Pittsburgh Sleep Quality score. Results: Intervention group participants reported significantly greater clinical improvement in global sleep quality than Control (p=0.016). These patients also exhibited significant improvements in component sleep disturbance (p=0.004), component sleep quality (p=0.015) and global sleep quality (p=0.032) after 3 months of supervised exercise intervention. Improvements in sleep quality correlated with improvements in depression (p<0.001) and six minute walk distance (p=0.04). When study results were examined categorically, with subjects classified as either "poor" or "good" sleepers, subjects in the Control group were significantly more likely to report "poor" sleep at 3 months (p=0.039) while Intervention participants were likely to report "good" sleep at this time (p=0.08). Conclusion: Three months of supervised, hospital based, aerobic and resistance exercise training improved subjective sleep quality in patients with heart failure. This is the first randomised controlled trial to examine the role of aerobic and resistance exercise training in the improvement of sleep quality for patients with this disease. While this study establishes exercise as a therapy for poor sleep quality, further research is needed to investigate the effect of exercise training on objective parameters of sleep in this population.

Not all systematic reviews are systematic : a meta-review of the quality of systematic reviews for non-invasive remote monitoring in heart failure

Remote monitoring for heart failure has been evaluated in numerous systematic reviews. The aim of this meta-review was to appraise their quality and synthesise results. We electronically searched online databases, performed a forward citation search and hand-searched bibliographies. Systematic reviews of remote monitoring interventions that were used for surveillance of heart failure patients were included. Seven (41%) systematic reviews pooled results for meta-analysis. Eight (47%) considered all non-invasive remote monitoring strategies. Five (29%) focused on telemonitoring. Four (24%) included both non-invasive and invasive technologies. According to AMSTAR criteria, ten (58%) systematic reviews were of poor methodological quality. In high quality reviews, the relative risk of mortality in patients who received remote monitoring ranged from 0.53 (95% CI=0.29-0.96) to 0.88 (95% CI=0.76-1.01). High quality reviews also reported that remote monitoring reduced the relative risk of all-cause (0.52; 95% CI=0.28-0.96 to 0.96; 95% CI=0.90–1.03) and heart failure-related hospitalizations (0.72; 95% CI=0.64–0.81 to RR 0.79; 95% CI=0.67-0.94) and, as a consequence, healthcare costs. As the high quality reviews reported that remote monitoring reduced hospitalizations, mortality and healthcare costs, research efforts should now be directed towards optimising these interventions in preparation for more widespread implementation.

Not all systematic reviews are systematic : a meta-review of the quality of current systematic reviews and meta-analyses for remote monitoring in heart failure

Background/aims: Remote monitoring for heart failure has not only been evaluated in a large number of randomised controlled trials, but also in many systematic reviews and meta-analyses. The aim of this meta-review was to identify, appraise and synthesise existing systematic reviews that have evaluated the effects of remote monitoring in heart failure. Methods: Using a Cochrane methodology, we electronically searched all relevant online databases and search engines, performed a forward citation search as well as hand-searched bibliographies. Only fully published systematic reviews of invasive and/or non-invasive remote monitoring interventions were included. Two reviewers independently extracted data. Results: Sixty-five publications from 3333 citations were identified. Seventeen fulfilled the inclusion and exclusion criteria. Quality varied with A Measurement Tool to Assess Systematic Reviews (AMSTAR scores) ranging from 2 to 11 (mean 5.88). Seven reviews (41%) pooled results from individual studies for meta-analysis. Eight (47%) considered all non-invasive remote monitoring strategies. Four (24%) focused specifically on telemonitoring. Four (24%) included studies investigating both non-invasive and invasive technologies. Population characteristics of the included studies were not reported consistently. Mortality and hospitalisations were the most frequently reported outcomes 12 (70%). Only five reviews (29%) reported healthcare costs and compliance. A high degree of heterogeneity was reported in many of the meta-analyses. Conclusions: These results should be considered in context of two negative RCTs of remote monitoring for heart failure that have been published since the meta-analyses (TIM-HF and Tele-HF). However, high quality reviews demonstrated improved mortality, quality of life, reduction in hospitalisations and healthcare costs.